Method of dyeing hair



Patented Got. 10, 1

2,359.33 METHOD or time 1mm John W. Orelup, Short Hills, N. J.

No Drawing. Application July 20, 1940, Serial No. 346,653

1 Claim.

This invention relates to improvements in the dyeing of hair and moreparticularly to the application of non-toxic preparations to dyeing andtinting of hair, which preparations produce high rubbing fastness of thedye on the hair and render useful for hair dyeing punposes a large classof non-toxic dyes heretofore unavailable for these purposes. Thisinvention is an improvement upon the invention of my copendingapplication Serial No. 195,539, filed March 12, 1938, which issued July23, 1940, as Patent No. 2,208,594, wherein is disclosed a process ofdyeing human hair which comprises the application of a pre-treatmentmaterial to the hair after which the dye is applied thereto.

I have now discovered new pretreatment materials the use of whichrenders much more satisfactory the results obtained from applyingnontoxic dyes to human hair. These pretreatment materials comprise saltsof cation active materials which themselves possess a desired degree ofcation activity. More specifically these material comprise salts ofreaction products of higher fatty acids with nitrogen containing loweraliphatic or alicyclic compounds having at least two basic reactinggroups.

Considerable advantages over prior art hair dyeing processes and overthe processes of my above mentioned copending application are effectedby the use of these new fixative materials in that non-toxic dyes may beapplied to the hair and are considerably faster to rubbing than dyeingsobtained in heretofore used processes and further in that the fixativesalts themselves have a beneficial effect on the hair and, beingcompletely soluble in water in the concentrations used, are easilyprepared for application and easily applied.

The fixative salts of my invention may be pared by reacting higher fattyacids with the nitrogen containing compounds at temperatures sufficientto insure that true condensations take place as evidenced by the removalof water or alcohol, and then by treating this reaction mixture with theproper acid to produce the desired salt. As starting materials tosynthesize the cation active fixative salts I may use acids ofpredominantly fatty character having at least 6 carbon atoms. Theseacids may be condensed with amino compounds of predominantly basiccharacter having at least 2 basic reacting groups such as amino orhydroxyl groups and preferably of lower molecular weight than the fattyportion of the compound. The condensation product thus obtained may beneutralized with any convenient acid.

As examples of fatty acids which may be used I may mention caproic,caprylic, capric, lauric, myristic, paimitic, cetic, oleic, stearic,ricinoleic, iinoleic, arachidic, behenic, lignoceric, palmitoleic,linolenic, eleostearic, clupandonic acids and mixtures of these acidsand others such as cocoanut fatty acids which contain substantialquantities of lauric, myristic, palmitic and oleic acids. These acidsobtained from cotton seed, corn, peanut, sun flower and similarvegetable sources may also be used.

Some of the amino compounds which may be used according to thisinvention may be represented by the following general formula:

in which R1, R2, and R3 may .be H, alkyl or aklylol and the sum of thecarbon atoms in R1 and R: is at least one. Specific examples of suchcompounds are Z-amino 2-methyl 1,3 propanediol and the highersubstituted homologues of the same compound such as th Z-amino 2 ethyl1,3 propanediol and the propyl and isopropyl compound, tris (hydroxymethyl) amino methane, Z-amino Z-methyl 1-propanol and the ethyl propyl,and iso-propanol substituted compounds, z-amino 1 propanol, iso-propanoland butanol, 2-amino 1,3 propanediol, B-amino 3-.

methyl 2-butanol, -amino S-methyl 3-hexanol, S-amino 4-octanoi. It willbe observed that these compounds are alcohols containing primary aminogroups. Of the polyamines I have found preferable the aliphaticpolyamines such as ethylene, propylene, butylene, amylene polyamines andtheir alkylated derivatives, as for example the dimethyl and diethylderivatives. The diamines, triamines, tetramines and pent= amines ofthis series have been found to be useful; I have found particularlyuseful diethylene triamine and triethylene tetramine. I may also usesuch nitrogenous compounds as pyridine, ethanol amines including themono-, diand triethanol amines and'various substituted derivatives ofthese compounds.

Some examples of convenient acids which may be used, in salt formationare formic, acetic, lactic, tartaric, butyric, phthalic, maleic, malic,sulfuric, hydrochloric, hydrobromic, succinic, propionic, phosphoric andothers. Of these acids I have found especially useful acetic andhydrochloric acids.

The process of preparing these pretreatment materials includes the stepsof reacting the amino compound with the fatty acid at tempera tures atwhich the condensation reaction will run at a reasonable speed andapplying direct ly to the reaction mixture on completion of thereaction, a suitable amount of acid to cause the pH of the mixture to bereduced to 6 to 6.5. As examples of such reactions I offer thefollowing, though it may be understood that these pies are not meant tolimit the scope of the invention but rather merely to illustrate oneembodiment thereof.

Example 1.In a reaction kettle are charged 210 lbs. of cocoanut fattyacids and 109 lbs. of 2-amino 2-methy1 l-propanol. The reaction mixtureis kept at a temperature of 175 C. for about six hours, at which timethe reaction is complete. Glacial acetic acid is now added to thereaction mixture until a test shows clear solubility in water at a pH of6 to 6.3. This acetate product is soluble in water and is used in from1% to 3% strength in water solution for direct application to the hair.With less effective results but with some useful properties obtaining inthe reaction product may be substituted any of the fatty acids mentionedabove in this example.

Example 2.141 lbs. of oleic acid and 58 lbs. of 2-amino 2-methyl 1,3propanediol are heated to 200 C. in a distilling kettle. The temperatureis allowed to go gradually to 215 C. over a space of an hour at whichtime the condensation is complete. Glacial acetic acid is now addeduntil the product has a pH in water solution of 6 to 6.5. A 1% to 3%solution of this product may be applied to the hair as a fixative inhair dyeing.

Example 3.210 lbs. of cocoanut fatty 'acids and 152 lbs. of triethylenetetramine are charged into a still and the temperature is raised to 175C. and then gradually over a space of about 4 color may oi'ten be moreconveniently obtained with the use 01' such compounds and the rubbingfastness of the dye on the hair be somewhat enhanced approximately inratio to the extent to which the salt formation has taken place.

The method of procedure in dyeing hair is as follows: A 2% aqueoussolution of the acetate of the condensation product of cocoanut fattyacid with 2-amino Z-methyl l-propanol is applied to the hair at roomtemperature. This solution is shampooed through the hair and allowed toremain for 15 minutes. The hair is then rinsed once and a 1 to 3%solution of naphthol blueblack thickened with gum .tragacanth is appliedand allowed to remain for twenty minutes. The hair may then be rinsedwith water until no color is seen in the wash water, whereupon theprocess is complete and the hair is dyed a solid black color.

Practically any desired color may be applied to the hair and any desirednon-toxic dye may be used. By employing such dyes I have been able toproduce a complete range of colors which hours to 185 C. At this timethe distillate or acid salt may be used in place of acetic acid in theseexamples.

Example 4.142 lbs. of stearic acid is mixed with 80 lbs. of triethylenetetramine and heated in a still to 180 C. The temperature is graduallyraised over a space of 4 /2 hours to 245 C.

at which time the distillate has amounted to 12 lbs. and the acid numberof the mass in the kettle has dropped to 1. This product, a crumblynearly white wax, is now treated with glacial acetic acid until a testshows clear solubility in water at a pH of 6 to 6.3. A 1% to 3% solutionoi. this acetate is used as a fixative in dyeing hair.

Example 5. --210 lbs. of cocoanut fatty acids is mixed with 113 lbs.diethylene triamine and heated in a still. The temperature is raised to150 C. then gradually to 190 C. taking 7 /2 hours. The distillateamounts to 17 lbs. The acid number of the mass in'the kettle is then 1.5and the condensation is finished. The'product is nearly white soft wax.The acetate is prepared as in the above examples. A l to 3% solution inwater is used as a fixative for the dye on the hair.

In some cases it has also been found desirable, as for example where thebasic compound selected has more than 2 basic reacting groups, to causethe salt formation to run only partially to completion. Such compoundsare often characterized by higher solubility in water which renderstheir use in professional beauty shops or in the home a matter of greatconvenience and ease.

' Furthermore it has been found that a desired are natural in tint andbeing non-toxic are noninjurious to the hair and scalp. Examples of dyeswhich give suitable shades are:

Dye Color index Durol Black 13 Direct Fast Brown M. Alizarine Brown 2R.Direct Fast Orange GC I do not, however, intend to limit my invention toany particular dyes as it will be understood that a great variety ofnon-toxic dyes are at my disposal; for example, polyhydroxylatedanthraquinones, sulfonated and carboxylated compounds and compoundscontaining sufficient hydroxyl groups to render them of predominantlyacid character, may be employed. By referring to the dyesabove-mentioned and others of generally similar character as non-toxic,it is to be understood that the dyes used are to be of such character,that, when applied to the hair in accordance with the directions hereingiven, they are not injurious to the hair or scalp of the averageindividual. Of course, particular individuals may be allergic to one oranother particular dye or class of dyes. This does not, however, make itimproper to characterize such a dye as non-toxic. As compared with thehighly toxic metallic salts and dyes of the phenylene diamine type whichhave heretofore been the only classes of dyes generally available forhair dyeing, the acid and direct dyes which I am able to use by my newprocess, are non-injurious and substantially non toxic.

Wherever the term neutral salt" is used in the claim, it is understoodto refer to salts which are substantially neutral for all practicalpurposes in application to hair.

I claim:

The method of dyeing hair which comprises the steps of rendering thehair receptive to nontoxic organic dyes by applying thereto a salt of acondensation product of a higher fatty acid and an alcohol containing aprimary amino group. and subsequently applying a water soluble nontoxicorganic dye containing negative salt forming groups.

JOHN W. ORELUP.

